Catalytic conversion of oxygenated organic compound mixtures



March 1954 K. L. HUJSAK ET AL 2,672,476

CATALYTIC CONVERSION OF OXYGENATED ORGANIC COMPOUND MIXTURES Filed June 29, 1949 Alcohols And Ketone s FRA CTIONATOR I 5 f 3 LL SCRUBBER 3 Q 1 .E fi 1- 3 SYNTHESIS UNIT c: (D o o o b- "l '0 G IN INV ENTORS KAROL L. HUJSAK RICHARD MUNGEN Patented Mar. 16, 1954 CATALYTIC CONVERSION OF OXYGENATED ORGANIC COMPOUND MIXTURES Karol L. Hujsak and Richard Mungen, Tulsa,

Okla., assignors to Stanolind Oil and Gas Company, Tulsa, Okla., a corporation of Delaware Application June 29, 1949, Serial No. 101,987

15 Claims. 1

Our invention relates to novel improvements in the art of manufacturing hydrocarbons and oxygenated organic compounds by the reduction of carbon monoxide with hydrogen in the presence of a catalyst. More particularly, it pertains to a method whereby the composition of an oxygenated organic chemicals fraction of the type obtained in the aforesaid reaction of carbon monoxide with hydrogen may be voluntarily controlled.

In accordance with the now generally practiced modification of the Fischer-Tropsch synthesis, carbon monoxide and hydrogen in a ratio of about 1:2 are introduced into a suitable reactor at temperatures of from 260 to 370 C. and pressures of the order of 150 to 550 p. s. i. and are catalytically converted into a product mixture containing hydrocarbons, oxygenated organic compounds, and water. Thereafter this mixture is further separated into a gas phase, a liquid hydrocarbon phase, and a water phase. While this reaction is generally associated with the synthesis of hydrocarbons, predominantly of the gasoline boiling range, or the synthesis of hydrocarbons which can readily be converted into a fraction boiling in the aforesaid range, such reaction is likewise a very valuable source of certain oxygenated organic chemicals including aldehydes, ketones, acids, and alcohols. This chemicals fraction may frequently constitute as much as 25 weight per cent or more of the total, viz., hydrocarbons plus chemicals, and is generally found to be substantially equally distributed in the hydrocarbon or oil and water phases. The quantity of chemicals involved in a reaction of this type may be further appreciated when it is realized that the daily production of total chemicals from hydrocarbon synthesis plants now designed for commercial purposes is of the order of 500,000 pounds. However, the complexity of such chemical mixtures, even after they have been split into oil and water soluble fractions, has apparently discouraged some of the principal workers in this field from attempting to isolate these materials in a substantially pure state. In the past a proposed solution to this problem has consisted of recycling the water soluble chem: icals back to the synthesis unit where they were dominantly to gasoline hydrocarbons. It has been further proposed to remove the oil soluble chemicals from the oil phase, for example, by extraction with a suitable solvent, separate the chemicals from the resulting extract and thereafter recycle them to the synthesis reactor Where they were converted chiefly into gasoline hydrocarbons. If, on the other hand, it was desired to recover the oil and water soluble chemicals fraction, this object was accomplished by means of a series of complicated chemical and physical separation steps. It will be apparent to those skilled in the art, however, that because of the extreme difficulty encountered in the separation of the complex chemical mixtures involved, viz., the separation of a single component from an azeotropic mixture in which the other components form azeotropes with one another as Well as with the component which it is desired to isolate, any system capable of satisfactorily accomplishing this object will add many thousands of dollars to the total construction cost of a commercial plant.

It is therefore an object of our invention to provide a method whereby the composition of the water soluble chemicals fraction, as well as the oil soluble chemicals fraction, if desired, may be controlled, thus rendering our process extremely flexible and making possible the production of only those chemicals that are economically attractive at current market conditions. A further object of our invention is to provide a method by which a selected class or classes of chemicals may be continuously produced to the exclusion of other classes of chemicals present in the feed mixtures employed.

Broadly, our invention contemplates subjecting chemical mixtures of the general type encountered in the hydrocarbon synthesis process to the action of hydrogen in the presence of" a catalyst at temperatures and pressures which may, although not necessarily, fall within the ranges employed in the hydrocarbon synthesis. Our invention, however, is not limited to the conversion of compounds typical of those produced by the aforesaid synthesis; but, on the contrary, is applicable to other compounds notproduced thereby but which belong to the same class or classes as those formed in hydrocarbon mixed with synthesis gas and converted preffsynthesis. In accordance with one embodiment of our invention, the mixture of chemicals is 3 introduced, together with from about 1 to 4 parts of hydrogen per part of feed, into a reactor of the general design employed in hydrocarbon synthesis where conversion occurs in the presence of a suitable fluidized catalyst such as, for example, a hydrocarbon synthesis catalyst, at a temperature of from about 125 to about 360 C. at pressures of 15 p. s. i. and higher. Thus, in accordance with our invention, an aqueous mixture of chemicals containing, for example, 8 per cent by weight of organic oxygenated compounds, at relatively low temperaturesand high pressures (125 to 175 '(land 200 to 600 p. s. i. or higher) when employing approximately one volume of hydrogen for each volume of feed mixture, there is obtained an increase in the alcohol content of said mixture'atthe exp'ense 'of the aldehydes present therein. The relative proportion of other components'inthe-systemfl rw mains substantially unchanged. However, if relatively low temperatures and pressures' (125 to 175 C. and 15 to about 100 p. s. i.) are employed together with the same ratio'ofhydro'g'en to feed mixture, the concentration of l'cetones is greatly increased at the expense of alcohols, aldehydes, and acids. Also, by employing both high temperatures and pressures (285 to 350 Land 200 to 600 p. s. i. and above), moderate increases in concentration of both alcohols and ketones at the expense of-aidehydes and acids are obtained. The ratio in which alcohols and ketones are produced may be varied by increasing the pressure or hydrogen concentration or both. The maximum temperature at which the reaotioncan be operated toproduceanincrease in yield of the desired class or classes of chemicals depends upon thecomposi-tion of the feed, the concentration of hydrogen,- and the pressure employed.

The-composition of the-chemical feed. mixture may vary widely; however, in the majority of instances-the feedshould contain-at least weight percent chemicals and at least5 weight per cent water. Ira-employing the process of our inventioni-n conjunction with the hydrocarbon synthesisrprocess, we have found it desirable to use feeds, viz., primary water (the aqueous phase in the original hydrocarbon synthesis product mixture) inwhich the chemicals (ketones, aldehydes, acids, and alcohols) are present to the extent-of from about- 5 to lfi weight per cent, usually" about 'ILE-weight per cent. In general, the majority of chemicals present inthe. primary water comprise essentially acetaldehyde; ethanol, acetic acid, and acetone with smaller amounts of isopropyl alco-- hol, n-butanol, methyl propyl ketone, methyl ethyl ketone, propionic acid, etc. Such compounds present in smaller amounts are hereinafter referred to as other chemicals. If desired, the-feed composition may be further varied by adding thereto substantially hydrocarbon free mixtures of aldehydes, acids, and alcohols derived from the oilsoluble fraction produced in hydro-- carbonsynthesis to obtain in increased concentration one or more of the classes of chemicals normally occurring in said oil soluble fraction. In addition to ieedmixtures of the composition indicated above, we may'likewise employ in the process of ourinvention mixtures consisting essentially of acids-in the' form of dilute, i. e., aboutfi weight/per cent, aqueous solutions or substantiallyxanhydrous mixtures of acids. Further more, individual acids may be utilized in dilute or relatively concentrated form. Thus, we have found that the acid. fraction derived from the first ste in the separation of the various classes of chemicals contained in the primary synthesis Water constitutes a highly satisfactory feed mixture. When employing such a feed, we have obtained high conversion of the acids over a hydrocarbon synthesis catalyst to aldehydes and alcohols.

While the process of our invention referred to above and more specifically described below is disclosed generally in terms of vapor-phase operation, it is to be strictly understood that we do not limit ourselves to such operating. conditions, inasmuch batch or" continuous liquid phase operations may be advantageously employed with various combinations of feed mixtures and catalysts as specifically illustrated by Example II. Also, in -carrying' out our invention the vapor phase conversion of oxygenated chemicals in accordarice therewith may, if desired, be effected in reactors having. fixed instead of fluidized catalyst beds.

The catalyst employed in efiecting our invention may be anyof several catalysts that have previously? been shown to be capable of promoting hydrogenation, including the known hydrocarbon synthesis catalysts as Well as other catalysts such as, for example, copper chromite,- pal-- ladium, platinum oxide, and. the like. In=fiuid-- ized bed operations the catalyst ispreferably employed in amounts such that the densityot-the catalyst bed rangesfrom about to -100. pounds per cu. ft, and preferably tea-bout pounds per cu. ft. in: thecase of iron. The catalystis: maintained a fluidized-state under the reac tion conditions employed by introducing the-feed mixture in vaporousformat a linearvelocity "of between about Oi -and 2'.0-ft.-per second. The concentration ofcatalyst employed: in liquidphase processes may vary widely and, ingeneralewill be determined by the activity ofthe particular cataw lyst employed. Thus, for example, with iron type hydrocarbon synthesis catalysts, We prefer to use approximately].- pound of catalyst for each 0.2 to 0.5 mole of reaction mixture. Other catalysts, such as palladium, platinum oxide, and the like, which are normally regarded as more-active=cat-- alysts-than' iron, may be employed in substantially lower' concentrations thanthose herein recommended ior iron. In this connection, while' temperatures ofat :least about C. are desirablewhen-:"employing hydrocarbon synthesis catalysts, temperaturesas low as about 20* C. may be' utilizedwith the more-active catalysts such as those just mentioned.

Our inventionmay be further illustrated by reference to the accompanying drawing where hydrogen and carbon monoxide in a' molar ratio of about two moles of hydrogen to one-mole oi carbon monoxide areobtained from asource notshown and introduced 'into synthesis unit '2 through linet. In-synthesisunit 2 the'rea'ctants' may be subjected to cont-act with: a catalyst such" as, for example, iron'mill-sca'le, in tho for nf of afluidized mass of finely divided solid particles;

5!. The reaction is effected: at temperatures of the order' of'260" to 360 C. and at press'ures inthe ide, etc., leave separator l0 through line I4 and are introduced into scrubber 16 where the gas phase is countercurrently contacted with water introduced at the top of scrubber is through line l8. Gases such as carbon dioxide, methane, ethane, etc., may, if desired, be partially recycled to feed line 4 via line 28 where they are mixed with fresh feed and introduced into synthesis unit 2. The balance of these products may be sent through line 2| to a recovery system (not shown) where the gaseous components are recovered and further refined, if desired. The water layer from separator l 0 is withdrawn through line 22 and transferred to saturator 24 where it is mixed with hydrogen introduced through line 26. The conditions prevailing in saturator 24 are preferably such that a vaporous mixture is obtained consisting essentially of 50 weight per cent hydrogen and 50 weight per cent primary water. To achieve vaporous mixtures in the saturator of the aforesaid general composition, temperatures varying from about 80 C. at p. s. i. to about 212 C. at 550 p. s. i. should ordinarily be employed. After the mixture of hydrogen saturated with primary water has been thus formed, it is withdrawn from saturator 24 through line 28 and introduced into preheater 30 where it is brought to reaction temperature, viz., 285 to 360 C., and thereafter introduced through line 32 into reactor 34 containing mill-scale catalyst in fluidized form. The temperature of reactor 34 is preferably maintained within the range of 285 to 360 C. however, pressures of from 15 p. s. i. to 600 p. s. i. or higher, may be employed, if desired. The product mixture is withdrawn from reactor 34 through line 36 and condenser 38 into separator 49 where the uncondensed products are withdrawn through line 42 and introduced into scrubber 44 Where they are countercurrently contacted with water introduced in the top of scrubber 44 through line 46. The uncondensed gas phase issuing from scrubber 44 and which consists essentially of hydrogen is transferred through line 48 where it is mixed with make-up hydrogen pumped in at the desired pressure by means of compressor 50 through line 52. The make-up hydrogen and recycle hydrogen from line 48 are then combined and introduced under pressure into saturator 24 via compressor 49 and line 26. In this connection, if desired, an additional source of hydrogen may be furnished in the form of a carbon monoxide-lean tail gas from line and introduced into line 26 where it is mixed with fresh hydrogen at the required pressure. However, if hydrogen from line 20 is to be employed along with makeup hydrogen in saturator 24, care should be exercised to prevent the introduction of tail gas from line 20 which contains in excess of from 2 to 3 per cent carbon monoxide. Higher carbon monoxide concentrations tend to promote the formation of hydrocarbons under the prevailing conditionsa result which it is our specific desire to avoid. The aqueous fraction in separator 40 containing water soluble chemicals and having alcohols or ketone's, or both, in increased ratio to v the remaining chemical components thereof is withdrawn through line 54 and combined with scrubber water in lines 55 and 58 from scrubbers l6 and 44, respectively, after which the combined fractions are conducted through reboiler 60 and introduced by means of line 62 into fractionator 64 where the alcohols or ketones, or both, may be taken ofiE overhead through condenser 66 and a portion of the condensate returned through line 68 to the top. of the column as reflux. Further purification of the overhead fraction thus ob' tained may be eifected in a known manner if considered necessary or desirable. The impurities separated from the ketones and alcohols may thereafter be combined with the primary water in line 22 and thus be converted into the desired products, as indicated above. The bottoms portion which represents a relatively concentrated mixture of chemicals is withdrawn from fractionator 64 through line 70 and may be, if desired, combined with primary water in line 22 and the resulting mixture introduced into saturator 24. By the foregoing expedient, all of the chemicals present in the primary water stream may be converted into the desired class or classes.

In the above-mentioned drawing reference to certain equipment such as pumps, gages, valves, and the like which obviously would be necessary to operate the process has been intentionally omitted. Only sufiicient equipment has been diagrammatically shown to illustrate the process, and it is intended that no undue limitation be read into our invention by reference to the draw, ing and description thereof.

Specific applications of the process of our invention to both liquid and vapor phase systems are further illustrated by the examples which follow.

EXAMPLE I A primary water stream from a hydrocarbon synthesis operation at 315 C. and 450 p. s. i. pres sure having the following composition was mixed at 82 C. and 15 p. s. i. pressure with hydrogen in a ratio of 1:1 and the resulting vaporous mixture introduced into a conventional hydrocarbon synthesis type reactor where said mixture was brought into contact with a fluidized iron catalyst. The catalyst Was maintained in a suspended turbulent state by introducing the reaction mixture at a linear velocity of about 1 ft. per second. The temperature of the synthesis zone during the reaction was maintained at about 0., while the pressure was held at about 15 p. s. i. Analysis of the synthesis tail gas indicated a product mixture of the following composition with a percentage gain in acetone of 250 weight per cent over that present in the original feed as shown below:

It should be noted that the fraction in both the reaction and product mixture designated as other chemicals did not change. In so far as total chemicals in this fraction are concerned, this is .true; however,

the proportion of ketones present a 7 thereimcomwrecmo that"in thefreantiowmixtflr wassmereasent essentially 'by' -the same ordn magnitude-aswasobservedlimthaeaseoaacetbnea- A primary water stream from; a rhydrocarbon synthesiswoperation at 1315 G. .andAEG -p.-s .'-i: pressure wasz-introdueedinto a :suitable 'hydmgena -P tion. apparatus-- containing; an ironrtype hydrocarbon' synthesis catalyst and-sealed, Thetem per-ature.-of the primary -'-Water was :thenbrOHghtto a-boutsl25fi (3., aiter which thepressurerwas increasedetoaapproximately 450 -p: vs.-i. by, the introduction'a'ofi hydrogen into the reaction -chamber. 'l'he resulting mixturercontained about one volume: of.-hydrogenwforeaoh-volumeof primarw wateraandihad fiche-followingapproximateacompm sitin-:--

oompdnent .2 a sound.

'IHeifon"catalystwasemployed in concentration' of approximately 1" pound of catalyst for each 0.2 to 015" f mole of the reaction mixture:

Duringthe course of the reaction, sufiicient v hydrogerr was introduced tovmaintain a pressure of approx-imately w p, s.-i. while the reaction mixture wasconstantly agitated. When the reaction reached completion; as evidenced by failiirerxofi' further hydrogen absorption, the 'react'ion'mixstdre was withdrawn fromthe apparattis and analyzed. Analysis indicated a product miitnr'e of "the following composition with a percentage gaii'r'r-in ettranol 30f: 33 weight percent ovefithatpresentrinathei originalrfed as shownxb'elowct Product- Mixture, Moles R, ea ction Mixture; Moles Percent Component Gain mmMPIJE- m A primary water stream from a hydrocarbon synthesis operation at 315 C. and 450 p. s. i; pressure-"was miXedi-witlii hydrogen in a ratio of 1:1 at 205 C.and' 450 p11 szi. pressure to produce a feed mixture having the" same" composition" asthat employed in Example L The resulting-mix ture'was then introduced into a' synthesis unit-at alinear velocity ofabout 1 ft, per second thereby-' ma'intainingthe ironflcatalyst presentinsaid'nn'it in-a-dense -suspended turbulent conditiom 'rna temperature of th e'synthesis' zone'during the re: action was mat'ainedat about 315C; while the pressure-was held at about 450 p: s; i.- Analysis- 0f;-the-synthesistailgasindicated-a produetrmix tureof. thesfollowing composition;-- with a percentage gaininethanol and acetone'rof- "and-:75'

weight percent; respectively; over-rthe:c0ncentra-- tior'x: on icompoundsfipresentiini the feed as=shownbelowz original Reaction" 'Pmchmt po ent Mixture; ,Mlxturd', Pggg Molesv Moles 7 Reaction" Component Mixture; I

Moles CHQGHO 08 KCHrUH QQH 53 01 130 0 0 l5 1, Hi0 1855? CH: 08- H F 80. 00-- G O: e 0' I Othenchemicals: 57

ysi V ttie syntriesrs tail gas 'indicateda prodfit mi 1311 f t H G pEJSiiEiCIITwith a lilf- Product I Mixture," f. lt'loles Reaction r 1 Minute;

Component The-example? which follows 4 demonstrates theability; of therprooess of oun invention; toficonvert mixtures of :acids .-into-a-1dehy des randralcohols in I accordancewith thee conditions herein set: forth:

A mixture-' 0? organicracidsf'im the-f'formr of a ;:4.5-weight percent:aqneousfsoliitiomsw percent of which consisted of acetic acid, 20 per cent propionic acid, and 20 per cent of butyric and higher acids, was mixed at 152 C. and 400 p. s. i. pressure with hydrogen in a ratio of four volumes of the latter to one volume of dilute acid solution. The mixture thus obtained was then introduced into a synthesis unit where it was brought into contact with a fluidized iron mill-scale hydrocarbon synthesis catalyst. The catalyst was maintained in a suspended turbulent state by intrcducing the reaction mixture at a rate of 64.5 S. C. F. H. per pound of catalyst. The temperature of the synthesis zone during the reaction was maintained at about 315 C. while the pressure was held at a level of about 400 p. s. i. Analysis of the synthesis tail gas indicated 92.5 per cent conversion of acetic acid, 96.5 per cent conversion of propionic acid and 95 per cent conversion of butyric and higher acids. The product mixture obtained had the following composition:

Product Mixture, Moles Component 1 Contained aldehydes and alcohols heavier than 04.

immaterial. In this connection it is to be strictly understood that the process of our invention may be employed in the production of alcohols and ketones in general, i. e., aliphatic, cycloaliphatic, aromatic, and the like. In general, it may be said that our invention covers a method for altering the concentration of one or more of the above-mentioned classes of compounds contained in a mixture thereof by treating said mixture with hydrogen under conditions such that the desired conversion is effected in the substantial absence of hydrocarbon synthesis.

What we claim is:

1. A process for increasing the proportion of at least one of the classes of compounds designated as alcohols and ketones present in a dilute aqueous mixture of aldehydes and carboxylic acids, which comprises contacting said mixture with a hydrocarbon synthesis catalyst in the presence of a gas consisting essentially of hydrogen at pressures which vary from about 15 to about 100 p. s. i. and at temperatures of from about 125 to about 175 C., where it is desired to increase the proportion of ketones, to a pres-- sure of at least about 200 p. s. i. within the above-recited temperature range where it is desired to increase the quantity of alcohols, whereby in accomplishing the aforesaid results from about 25 to about 95 per cent of the acids present in said mixture are converted into at least one of said classes of compounds, and recovering a mixture in which at least one of the classes of compounds designated as alcohols and ketones is present in increased ratio to the aldehydes and acids originally present in said aqueous mixture.

2. A process for increasing the proportion of at least one of the classes of compounds designated as alcohols and ketones present in a dilute aqueous mixture of aldehydes and carboxylic acids, which comprises contacting said mixture with an iron hydrocarbon synthesis catalyst in the form of a fluidized bed in the presence of a gas consisting essentially of hydrogen at pres sures which vary from about 15 to about 100 p. s. i. and at temperatures of from about 125 to about 175 C., where it is desired to increase the proportion of ketones, to a pressure of at least about 200 p. s. i. within the above-recited temperature range where it is desired to increase the quantity of alcohols, whereby in accomplishing the aforesaid results from about 25 to about per cent of the acids present in said mixture are converted into at least one of said classes of compounds, and recovering a mixture in which at least one of the classes of compounds designated as alcohols and ketones is present in increased ratio to the aldehydes and acids originally present in said aqueous mixture.

3. The process of claim 2 in which a dilute aqueous mixture is employed containing from about 5 to 15 weight per cent of ketones, aldehydes, acids, and alcohols.

l. A process for increasing the proportion of at least one of the classesof compounds desig-, nated as alcohols and ketones present in a dilute aqueous mixture of aldehydes and carboxylic acids, which comprises contacting said mixture with an iron hydrocarbon synthesis catalyst in the liquid phase and in the presence of a gas consisting essentially of hydrogen at pressures which vary from about 15 to about p. s. i. and at temperatures of from about to about -C., where it is desired to increase the proportion of ketones, to a pressure of at least about 200 p. s. i. within the above-recited temperature range where it is desired to increase the quantity of alcohols, whereby in accomplishing the aforesaid results from about 25 to about 95 per cent of the acids present in said mixture are converted into at least one of said classes of compounds, and recovering a mixture in which at least one of the classes of compounds designated as alcohols and ketones is present in increased ratio to the aldehydes and acids originally present in said aqueous mixture.

5. A process for increasing the proportion of at least one of the classes of compounds designated as alcohols and ketones present in a dilute aqueous mixture of aldehydes and carboxylic acids, which comprises condensing a vaporous.

product mixture from ahydrocarbon synthesis into an oil phase and a water phase, separating said phases, thereafter contacting. said water phase containing aldehydes, alcohols, ketones.

aura-4cm l1? accomplishingtthe atoresaridcresultsrairormrabonti r-to about 95'ipenxfcent of the aoidsiipresent: said mixture' are :fconvertedrinto atileasts onenof said classesof conrpounds; :and'recoveringia 1mintureiniwhichzat least zone 'of "the classeszofacompoundsiwdesignateda'as alcohols and 1*..ketones e iSi present in increased ratio to the aldehydesxandz acids-originallygpresentinzsaid:aqueous mixture.

'GJJKA. process-:for increasing-the proportion." of. atkle'astmne ottheclassesof compounds.:designated asoilesoluble alcohols :andrketones presentin. the-mixturezofroilssoluble aldehydes and carbox yliciacids-,-.-whichi comprises contacting said mix ture withiaihydrocarbomsynthesis catalystin the presence ota=gas-consisting :essentiallyoihydroegen air-pressures which vary from about 15wto about 1109 '1.-p;.=s;; i. and at temperatures-of. from about! 1-259. toabout 175 C-., where'iitis desired toincreasei-theiproportion :of :ketones; to a pressure oiaat leastwaboutYZOO"p: is. i. with-in: the .aboveueecited temperature range evhere it .is-.desi redwtoin-. crease ewe-quantity. oft-alcohols; whereby in: accomplishing the zaforesaid'resultst from? about 5: toaabout 95 Fper cent-.of-rtheacids' ipresent in sai'd mixture ;are converted into .ateleastone of said' classes lof-lcompounds, and-.rrecovering :mixture in.which ateleastaoneof therclassesvofl-compoundsdsisnatedeasi-alcoholsl BIIQ KGtOIIGSriST present-in.- increasedmatimto thevaldehydes andiacids-orign nally presentdn said aqueous mixtures- JLHA procession increasing itheaconcentnation alcohols-andketonespresent incaidilute aqueous; mixture containingsaldehydes and: acids, which comprises contacting .saidimixture withta hydrogenation catalystinthe.presenceof la gas consistinglessentially. of. hydrogen at .a temperature-oi Irom about 285?. to about-3599c. at pres-- sures .otaboutzou .to. fiOO-p. s. i., .and recoveringalc'ohols' and-ketones: .iniincreased ratio "to acids andil. aldehydes .present. ..in.. the mixture thusv treated;

BAA. procession increasing: the concentration of alcoholsi-andketones present inla -dilute aqueous-fraction containing. aldehydes. and acids, whichrcomprises.:contacting. said fraction-with an .iron. hydrocarbon. .synthesiscatalyst. in the. presenceota gassconsisting essentially of hydro geniat. a temperature -of.-from aboutl- 285 to about. SKOFI CL .at pressures .of about. .2010 .to 600.1), :s. :i. whereby... saidcaldehydes. and .acids..:are at. least. partiallitconverted .into alcohols and .ketones,.-re-.. covering alcohols. and .ketones iniincreasedn'atio tdaldehydes and acidspresent inlsaidwfraction, separating said. 'alcoholsand .ketones ir'oin .said fraction, .-and-repeating.,.the above cycle :by subs. j ect'ing said .Zfr'aotio'n. .containiug...aldhydes .and acids to catalytic hydrogenation underthe aforesaid conditions .of. .temperature and pressure.

T9." .A pro'cessior increasing theconcentration of alcohols .present in a. dilute. .aqueous. fraction. containing acids and .aldehydes, whichlcomprises contacting said ifr'action with ,an. iron. hydrocan bonzsynthesis catalyst in the-presence .ofracgas consisting ,essentiallir of .hydrogen .at .a tempera ture .of .fromabout 125 toabout 175 'C. and at apressureof ffrom about 200' to 'SOU p s. i. Whereb'yisa'id ,aldehyde'sare at least partially converted into. alcohols and-whereby fromabout .65 to about 95 per cent .of'said acids are converted into .alcohols' and recovering said alcohols in increased ratio .to aldehydes. and racids.

100A processifor increasingsthe.concentration oiiketones present in a .:dilute-..aqueous.zfraction alcoholsyaldehydes, :andacids, which comprisesi'contactingesaid fraction with andron hydrocarbon: synthesis 1 catalyst in 1 :the: presence of: :a l gas :consist-ing j essentially '-of hydrogen. at :a' temperature of from about 125 to about 175--'C; and at a pressure of tfrom about 15' to about p. s. i. whereby said alcohols; aldehydes; and acids are at least partially converted into ketones; and recovering-said .ketones' in increased ratio to :al-- cohols; aldehydes, and acids.

ill-A process for converting to ketones: the aldehydes, alcohols; and acids present in iaudilute aqueous mixture thereof, whichcomprises: contacting said mixture with a hydrocarbon thesis catalystin the presence -of=agas consistingv essentially of hydrogen at .a temperature of from about 125 to about C; and-at a pressure 'of fromiabout 15-t0about 100 p. s; i. -wherebygsaidaldehydes, alcohols; and acids 'are at least pan tially converted into -ketones, recovering said' lie-- tones .in increased. ratio to the -.remaining mixture ofaldehydes, alcohols, and acids, separating said ketones from said mixture, thereafter contacting said mixture with a hydrogenation cataly'stiunde'r the aforesaid .conditions of temperatureand pressure to produce additional quantities of-fiketones; separating the ketonesthus formed, and repeating the above cycle until isubstantiallyall of the aldehydes, acids andaalcohols have beenconverted into ketones.

12. A processfor substantially. completely converting to alcohols the aldehydes and acids present; in a hydrocarbon synthesis...primary water: fraction, which comprises contacting 'said fractionwith-a hydrocarbon synthesis catalyst in the presence of'a 'gas consisting essentially of hydrogen at a temperature oiiromabout 125 to about 1-75?- C. and-at 'a-upZ'GSSUIB of-ifircnmaboutQOG-flzo aboutfiOO-p; s..i., wherebyifroin abouta65- to'about' 95 1per :cent ofthe acids-present: inisaidwprimary Water-inaction rare -.converte'du-intozalcohols, irecovering saide alcohols :invincreased ra tio to ralde 'hydes rand acidsnpresent. in: said: inaction;,:sepa.-

rating alcoholsuifromwsaid fraction; thereafter contacting the ml'atter with a1 (hydrocarbon: thesis catalyst: under the :aforesaid conditions of temperature and pressure to {pro duce-zadditional quantities of ;alcoh0ls,=an'durepeatingcthe above cycle until substantially .all'of: saidialde'hydes: and acids have been-substantiallycompletelyconverta ed intoalcohols.

1-3; Inna process for converting a :mixture 20f organic :acids to aldehydes' and-alcohols, the step which comprise --contaoting-.said mixture with: a

hydrocarbon. synthesis scatalyst :inthe. presence ofa-gas .consisting :essentially tvo fshydro'genzzat :a: temperaturepfifrlom iabout 285": abouttflGO-t C; at pressures: of 1200 p; :s..: i. and above; :whe'reby up :to :from about 92 120 :about 96 pen cent 'of the organic acids present in: said-mixture are convert-' ed into aldehydes and alcohols;

"14. -A "pro'ccss'ior increasing the concentration of' alcohols present in a dilute aqueous fraction: containing aldehydes'and acids, which-comprises contacting said fractionwith an iron hydrocar bon'synthesis catalyst the liquid phase'and in the presencebf a' gas consistingessentially'of hydrogen at "temperaturesof from-'about' to about C. and at pressures of from about 200 to about 600p; sxi. whereby aldehydes are at least partially converted :into alcohols and whereby fromabout 65 to about-95 per cent ofsaid'acids present. in said fraction areiconvertedzinto alco hols, .and recoveringwsai'd alcohols in increased ratio .to .aldehydes. and. acids.

15 Aprocess .for increasing-Jone concentration.

13 14 of ketones present in a dilute aqueous fraction References Cited in the file of this patent containing aldehydes, alcohols, and acids, which UNITED STATES PATENTS comprises contacting said fractlon with an 1ron Number N e D t catalyst in the liquid phase and in the presence of a gas consisting essentially of hydrogen at a 5 15841640 sfmmldt et a1 sept- 1928 temperature of from about 125 to about 1'75" C. 1,979841 Pler et a1 61 1934 and at a pressure of from about 15 to about 100 2059495 Smeykal 1936 p. s. i. whereby alcohols, acids, and aldehydes 2171324 Zetzsche 1939 are at least partially converted into ketones, and 2:205184 Woodhouse June 18, 1940 recovering said ketones in increased ratio to al- 10 2464916 Adams et a1 1949 cohols, aldehydes, and acids 2,516,940 Arnold et a1 Aug. 1, 1950 2,516,958 Coley Aug. 1, 1950 KAROL L. HUJSAK. 2,543,038 McGrath Feb. 2'7, 1951 RICHARD MUNGEN. 2,569,380 Holder Sept. 25, 1951 

1. A PROCESS FOR INCREASING THE PROPORTION OF AT LEAST ONE OF THE CLASSES OF COMPOUNDS DESIGNATED AS ALCOHOLS AND KETONES PRESENT IN A DILUTE AQUEOUS MIXTURE OF ALDEHYDES AND CARBOXYLIC ACIDS, WHICH COMPRISES CONTACTING SAID MIXTURE WITH A HYDROCARBON SYNTHESIS CATALYST IN THE PRESENCE OF A GAS CONSISTING ESSENTIALLY OF HYDROGEN AT PRESSURES WHICH VARY FROM ABOUT 15 TO ABOUT 100 P. S. I. AND AT TEMPERATURES OF FROM ABOUT 125* TO ABOUT 175* C., WHERE IT IS DESIRED TO INCREASE THE PROPORTION OF KETONES, TO A PRESSURE OF AT LEAST ABOUT 200 P. S. I. WITHIN THE ABOVE-RECITED TEMPERATURE RANGE WHERE IT IS DESIRED TO INCREASE THE QUANTITY OF ALCOHOLS, WHEREBY IN ACCOMPLISHING THE AFORESAID RESULTS FROM ABOUT 25 TO ABOUT 95 PER CENT OF THE ACIDS PRESENT IN SAID MIXTURE ARE CONVERTED INTO AT LEAST ONE OF SAID CLASSES OF COMPOUNDS, AND RECOVERING A MIXTURE IN WHICH AT LEAST ONE OF THE CLASSES OF COMPOUNDS DESIGNATED AS ALCOHOLS AND KETONES IS PRESENT IN INCREASED RATIO TO THE ALDEHYDES AND ACIDS ORIGINALLY PRESENT IN SAID AQUEOUS MIXTURE. 